Stannanediol derivatives



Patented July 27, 1954 STANNANEDIOL DERIVATIVES Gerry P. Mack, JacksonHeights, N. Y., and Ferdinand Bernard Savarese, Westwood, N. J.,assignors to Advance Solvents & Chemical Corporation, New York, N. Y.

No Drawing. Application October 8, 1952, Serial No. 313,806

7 Claims.

The invention relates to new organometallic tin compounds.

The new compounds correspond to the formula R 2 wherein R and R standfor the same or different monovalent hydrocarbon radical, OR. is analkoxy radical and Z is the radical of a monocarboxylic acid or of adior polycarboxylic acid in which allcarboxylic groups but one areesterified with an alcohol.

These compounds may be designated as etheresters ofhydrocarbon-substituted stannanediols, i. e. such stannanediolderivatives in which one hydroxyl group of the stannanediol issubstituted by an alkoxy radical and the other hydroxyl group by theradical of a monocarboxylic acid or of a halfester of a dicarboxylicacid or of a polyester of a polycarboxylic acid having n carboxylic acidgroups of which (n-l) groups have been esterified with the same ordifferent alcohols. a

The general procedure for preparing the new compounds consists inreacting an organo-tin dihalide with an alcoholate of the alcohol whichhas'to form the alkoxy group, and with a. salt of a monocarboxylic acidor of a halfester of a dicarboxylic acid or of a diester of atricarboxylic acid. Such salt should have a cation forming halides whichare insoluble or diflicultly soluble in the solvent, such as alkali,earth alkali, or ammonium. As solvent, we use preferably the anhydrousalcohol of which the alcoholate is a component of the reaction mixture.

The reaction takes place according to the following equations:

R R SMOR (O2CCR. (COzRfi) n) +2MeX wherein R R and OR have the samesignificance as in Formula 1; R is hydrogen or the hydrocarbon residueof a monocarboxylic acid, R is the hydrocarbon residue of a diortricarboxylic acid, R is the residue of an alcohol esterifying thecarboxylic groups, n is 1 or 2, X is halogen and Me an alkali oralkaline earth metal.

Water is undesirable during the reaction, and we use therefore anhydroussolvents and reactants. The salts of the employed acids or partialesters are preferably prepared by neutralization of the carboxylic groupwith a sodium alcoholate according to the reaction Rc'OzI-liiNaOR-aRCOzNai-R oI-l But other neutralizing agents can be used as forexample sodium hydroxide or metallic sodium or potassium.

A convenient procedure consists in dissolving the calculated amount ofsodium metal in the anhydrous alcohol employed for furnishing the alkoxygroup of the end product, and adding the calculated amount of themonocarboxylic acid or of the dior polycarboxylic acid, of which all butone carboxylic groups are already esterified, to the sodium alkoxidesolution under cooling to prevent saponification of the ester group.When then an organo-tin dihalide is added to the solution, the reactionas indicated above in Equations 2 or 3 takes place. The sodium halideformed in the reaction is removed and the solvent distilled off underreduced pressure.

The stannanediol ether esters thus obtained are soluble in most organicsolvents such as alcohols, ketones, esters, aromatic hydrocarbons, alsoin a wide variety of plasticizers used in the compounding of vinylresins. They can be polymerized to form polystannanediol ether esters ofthe formula n snwn-z wherein R R R and Z have the same significance ashereinbefore and n designates the degree of polymerization. A suitablepolymerization procedure is a heat treatment in the presence ofmoisture, as disclosed for stannanediol diesters and diethers in thecopending application, Serial No. 132,406, by Gerry P. Mack and EmeryParker, filed December 10, 1949, now Patent No. 2,628,211.

The new compounds contain three different types of groups, 1. e. (l) thehydrocarbon groups R and R directly linked to the tin atom, (2) thealkoxy group CR and (3) the carboxylic acid radical Z. Each of thesegroups can be varied and a very large number of such compounds can beprepared. We shall not attempt to list all the possible startingmaterials and combinations but we will give, in the followingdescription, a selective list of reactants which may be used inreactions as defined in the Formulas 2 and 3, and we shall then describein the examples some compounds illustrative of the new group oforganotin compounds. It should be understood that these examples are notgiven to limit our invention in any way.

The R and R, groups of the above formulae are furnished by organo-tindihalides R RFSnXz, in which R and R may be different but will begenerally the same as the latter halides are more readily available incommerce and as the nature of these R, groups has in most cases no orlittle influence on the properties of the ether esters which arecontrolled by the nature of the ether and ester groups, B and Z. R and Rmay be, for instance, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl,lauryl, allyl, benzyl, phenyl, tolyl, cyclohexyl; X is C1 or Br.

As the alcohol component, we can use aliphatic, cyclic or aromaticalcohols, also ether and thloether alcohols, such as methanol, ethanol,propanol, allyl alcohol, butyl alcohol, octyl alcohol, oleyl alcohol,furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, cinnamylalcohol, phenylethyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol,butoxyethyl alcohol, methyl hydroxyethyl sulfide, ethyl hydroxyethylsulfide and others.

The acid component can be an aliphatic aromatic or alicyclic saturatedor unsaturated monocarboxylic acid such as formic, acetic, propionic,butyric, valeric, Z-ethylhexoic, caprylic, lauric, myristic, stearic,acrylic, crotonic, oleic, linoleic, ricinoleic, sorbic, furoic, benzoic,cinnamic, phenylacetic, fencholic, cyclohexylacetic, cyclohexylbutyricacid, and other acids.

As stated hereinabove, also any polycarboxylic acid can be used for thereaction, provided that only one of the carboxylic acid groups is freeor in the form of the salt and that all the other carboxylic acid groupsare esterified with one or more of the alcohols enumerated above for theintroduction of the alkoxy group. Therefore, We can employ the halfesterof dicarboxylic acids, such as malonic, succinic, glutaric. adipic,sebacic, fumaric, maleic, itaconic, citraconic, phthalic,hexahydrophthalic, 3,6-endomethylene tetrahydrophthalic,3,6-endoxotetrahydrophthalic, camphoric acid and other acids. In thesame way, tricarboxylic acids such as citric acid, tricarballylic acidand the like can be employed if two of the acid groups are in theesterified state.

Example 1 53.9 g. of lauric acid (0.25 mol) having a molecular weight of215.6 were dissolved in 500 cc. of anhydrous methanol and neutralizedwith 27 g. of sodium methoxide (0.5 mol) dissolved in 250 cc. ofmethanol.

The resulting soap was finely dispersed in the methanol by high speedstirring and then 76 g. of dibutyl tin dichloride (0.25 mol) dissolvedin 100 cc. of methanol were added to the soap-sodium methoxide solutionat 25 C. and stirred until the batch was neutral. The salt formed in thereaction was filtered oil" and the methanol distilled off. The residualoily tin compound was purified by dissolving it in cold benzene and byfiltering off the impurities, and it was recovered by removing thebenzene by vacuum distillation. The obtained viscous liquid (specificgravity 1.1260; ref. index 1.4860) corresponded on the basis of its tin,methoxy and lauric acid content (found: Sn=25.0%, CH3O:6.4%,C11H23COOH=45.3%), to the formula The amount of sodium chloride obtainedwas 29.5 g. corresponding to the theoretic amount.Dibutyltinmethoxylaurate requires theoretically 4 24.81% of tin, 6.5% ofmethoxy and 45.15% of lauric acid.

Example 2 4.6 g. of sodium metal were dissolved in 400 cc. of n.butanol, and 28.3 g. of oleic acid were added to this solution. Thesolution so obtained was reacted with 68.8 g. of diphenyl tindichloride. After the completion of the reaction the salt and the excessbutanol was removed; the last traces of sodium chloride were eliminatedby dissolving the residue in benzene, filtering and removing thesolvent. The soft waxy product obtained was diphenyltinbutoxyoleate andcorresponded to the formula:

as substantiated by the tin, oleic acid and butoxy content of thecompound.

Example 3 In an identical manner as described in the previous examplesdiethyl tin ethoxyethoxide crotonate was prepared by reacting 49.5 g. ofdiethyl tin dichloride with an equimolar mixture of sodium crotonate andsodium ethoxyethoxide, prepared by dissolving 9.2 g. of sodium metal ina large excess of ethylene glycol monoethyl ether. and adding 17.2 g. ofcrotonic acid to this solution. The salt formed in the reaction wasfiltered off and the excess ethyleneglycol monoethyl ether was removedby vacuum distillation. The resulting liquid product had, afterpurification, the formula (Theory: Sn=33.82%; crotonic acid=24.52%.Found: Sn:33.71%; crotonic acid=24.70%.

Example 4 81 g. of sodium methoxide (1.5 mols) were dissolved in 750 cc.of cold methanol, and 98.6 g. of monomethyl maleate (0.75 mols) wereadded slowly under cooling at 0 C. The clear solution thus obtained wasreacted with 227.8 g. of dibutyl tin dichloride (0.75 mol) under coolingand stirring at O-5 C. and. stirring was continued until the mixturebecame neutral. The salt formed in the reaction was removed byfiltration; then the methanol was distilled off and the residual oilextracted with cold toluol. After distilling off the toluol, a liquidproduct (spec. gravity=l.3740; refr. index=l.5103) was obtained whichwas dibutyl tin monomethoxy methylmaleate and had the formula (Theory:Sn=30.21%; CH3O=15.79%; ma i acid=29.54%. Found: Sn=30.70%;

CH3O= 15.83%; maleic acid=29.80%

In an identical manner the following products were prepared:

Sp. gravity:1.3250 Refr. index:1.5068 Tin required:27.29% Found:28.09%Methoxy required-:6.97% Found=7.05%

Dibutyl tin monomethoxy allyl maleate which corresponded to the formulaCiHn \OGHI Spec. gravity:1.2910 Refr. index:l.5011 Tin required:28.34%Found:2'7.99% Methoxy required:7.41% Found:7.27%

Dibutyl tin monomethoxy tetrahydrofurfuryl maleate which had the formulaTin required:25-.64% Found=25.3% Methoxy required=6.7% Found:6-.58%

Dibutyl tin methoxy oleyl maleate of the formula wherein R representsthe radical CH3 (CH2) 7CH CH CH2) 8 (9-octadecenyl) Spec. gravity at 250.:1.1290; refr. index at 25 C.:1.4882; tin required, 18.85; found,19.0.

Dibutyl tin monomethoxy methyl succinate of the formula C HoOOOCHaOHzCOOCHa Spec. gravity=1.3500 Refr. index:1.4980

Tin required:29.67 Found=29.80% Methoxy required: 15.48 Found: 15.40%

Dibutyl tin monomethoxy methyl phthalate which had the formula OOOCH;

04KB O O C 6 Spec. gravity:1.3700 Refr. index:1.5448 Tin required:26.8%Found:26.7% Methoxy required=14.01% Found:13.95%

Diethyl tin monoethoxy ethyl sebacate which had the formula 0211i/:OOC(CH2)ACOOC2H5 C2H5 OCrHs I Tin required:26.3%; found=26.0%.

Diphenyl tin monomethoxy butyl itaconate having the formula 00H;OOCCHzCCOOCiHQ /Sn\ OeHs O CH:

Tin required=24.26 Found: 24.50 Methoxy required:6.35 Found:6.22

Example 5 This example is given to illustrate the preparation ofhydrocarbon substituted polystannanediol alpha, omega ether esters.

27.0 g. of sodium methoxide and 41.0 of anhydrous sodium acetate in theform of a fine powder were slurried in 500 cc. of dry benzene. 303.8 g.of dibutyl tin dichloride dissolved in 250 cc. of dry benzene weredropped in under vigorous stirring and cooling at 10-20 C. Stirring wascontinued for several hours after the addition was completed, until afiltered sample did not contain chlorine. The sodium chloride wasfiltered off and the benzene distilled off under reduced pressure at20-30" C. The remaining colorless liquid corresponded to the formula:

CiHo OCH:

0411f -1 OOCOH;

which requires:

Found:36.70% Found:9.53 Found: 19.05

50 g. of this dibutyl tin methoxy acetate were placed in a flask andmoist air was blown through the liquid at -100 C. and the gases werecondensed. The condensate contained methanol and acetic acid; the liquidresidue solidified on cooling to a waxy solid easily soluble in organicsolvents. According to the analysis of this solid, it had the formula:

7 voltaility with steam of the alkoxy or fatty acid groups in thestarting material.

The new compounds have various uses and are particularly suitable asstabilizers to protect halogen-containing resins' against deteriorationand discoloration due to the influence of heat and light. Suchstabilized resins are disclosed and claimed in our copending patentapplication, Serial No. 151,524, filed March 23, 1950, now Patent No.2,631,990, of which this application is a continuation-in-part.

Various modifications of the invention, other than specificallydescribed herein, will be evident and are included within the scope ofthe appended claims.

What we claim is:

1. As a new composition of matter, the ether ester of a monomerichydrocarbon-substituted stannanediol of the formula 3 OOCCH wherein Rand R represent alkyl radicals and R and R are monovalent aliphatichydrocarbon radicals.

3. Dibutyl tin monomethoxy methyl maleate of the formula H30 0 c on 4.Dibutyl tin methoxy oleyl maleate of the formula 1 ROOCCH c4119 OOCCHwherein R is the 9-octadecenyl radical.

' 5. Linear hydrocarbon-substituted 'polystannanediol ether esters ofthe formula wherein R and R are monovalent hydrocarbon radicals, OR isan olkoxy group, Z is a carboxylic acid radical selected from the groupconsisting of monocarboxylic acid radicals and polycarboxylic acidradicals having not more than three carboxyl groups, of which all butone of the groups are blocked by esterification, and n is a numeralhigher than 1, designating the polymerization degree.

6. A method of preparing hydrocarbon-substituted stannanediol etheresters which comprises reacting in an alcohol an organo-tin dihalide ofthe formula R R SnX2 wherein R and R are monovalent hydrocarbonradicals, and X is a halogen selected from the group consisting ofchlorine and bromine, with an alkali metal a1- coholate of said alcoholand the salt of a carboxylic acid selected from the group consisting ofmonocarboxylic acids and polycarboxylic acids having not more than threecarboxyl groups,-of which all but one of the groups are blocked byesterification, the cation of said salt being selected from the groupconsisting of alkali and ammoni- 7. A method of preparing linearhydrocarbonsubstituted polystannanediol ether esters comprising heatinga monomeric hydrocarbon-substituted stannanediol ether ester in thepresence or moisture, said stannanediol ether ester having the formulawherein R and R are monovalent hydrocarbon radicals, OR is an alkoxygroup, and Z is a carboxylic acid radical selected from the groupconsisting of monocarboxylic acid radicals and polycarboxylic acidradicals having not more than three carboxyl groups, of which all butone are blocked by esterification.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,307,092 Yngve Jan. 5, 1943 2,489,518 Burt Nov. 29, 19492,631,990 Mack et al Mar. 17, 1953 OTHER REFERENCES Chem. Ab., v01. 10,page 1253 (1914)

1. AS A NEW COMPOSITION OF MATTER, THE ETHER ESTER OF A MONOMERICHYDROCARBON-SUBSTITUTED STANNANEDIOL OF THE FORMULA